CN109734699A - Polymerizable II type photoinitiator of one kind and preparation method thereof - Google Patents
Polymerizable II type photoinitiator of one kind and preparation method thereof Download PDFInfo
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Abstract
The invention discloses polymerizable photoinitiators being shown below and preparation method thereof, such initiator not only increases its compatibility with Photopolymer System, in Light Curing, greatly reduce the residual of initiator, it is alternatively arranged as the monomer of synthetic macromolecule photoinitiator, therefore, it is had broad application prospects in curing field.
Description
Technical field:
Content of the present invention is a kind of new polymerizable II type photoinitiator and preparation method thereof.
Background technique:
UV-curing technology is the environmentally friendly green technology in one of fields such as coating, ink, adhesive, with biography
The ratio containing dicyandiamide solution of system, UV photocuring technology have the outstanding features such as solvent-free discharge, high-efficient, energy saving.Body of material one
As be made of oligomer, monomer and photoinitiator, all solidify under enough action of ultraviolet light, with UV photo-curing material application
It is more and more extensive, there are some unexpected problems, and free radical caused by initiator itself without initiation activity or draws
Hair activity is lower, remains in cured film after being quenched, and residual initiator becomes to the toxicity that generation is precipitated in surface migration to be used
Potential major hidden danger in journey.
For food packaging, an important problem of concern is the migration of the compound of cured layer and packaging material and mentions
It takes.Migration is the process that compound is directly transmitted in cured layer and packaging base material, and this migration may cause packing timber
The deterioration of the physical property of material, but more importantly compound can also be moved to further in food, many compounds itself
Toxicity is little or does not have toxicity, but becomes toxic when a large amount of use.It is minimum in food packaging in view of health hazard
The amount for changing transportable object and extractable is very important problem.
In order to abide by the following tightened up legislation demands that may be formulated, more for health requirements, photoinitiator will also have
Very low migration and solvent extraction rate, and photoinitiator has from a variety of volatility released in Light Curing
The concentration of evil organic compound will also have stringent restriction.In order to further decrease its mobility and volatility, draw in addition to increasing
The molecular weight of agent is sent out to reduce diffusion velocity, such as Multifunctional initiator, polymerization initiator；Still an alternative is that increasing it
Reactivity is this kind of to draw at effective way to solve this problem to make it build up converging network, such as polymerizable initiator
Hair agent is simultaneously containing optical active group and unsaturated group in molecule, and under the irradiation of UV light, initiator also polymerize itself
Form a part of polymeric membrane, under such initiator small molecule residual, with resin compatible is good, nonmigratory problem.
Summary of the invention:
The object of the present invention is to provide a kind of polymerizable photoinitiator and preparation method thereof, polymerizable light of the present invention
Initiator and preparation method thereof have the advantage that 1) prepared by polymerizable photoinitiator to cause activity high, 2) it is compatible with resin
Property is good, 3) migration is small.
A kind of polymerizable photoinitiator provided by the invention, structural formula are (I):
Wherein: R is selected from H, C1-C4 alkyl.
The preferred having structure of Formulas I:
The preparation method of formula (I) compound provided by the invention, can be carried out with following reaction equations:
Wherein: R is selected from H, C1-C4 alkyl.
The preparation method of formula (I) compound provided by the invention comprises the following steps that
1) pentaerythritol diacrylate replaces chloracetyl chloride (IV) to react generation formula (II) under alkaline condition with alkyl
Compound；
2) above-mentioned formula (II) compound 1) obtained under the action of catalyst and polymerization inhibitor with corresponding 4- thioxanthones first
Esterification reaction obtains formula (I) compound.
The preparation method of formula (I) compound provided by the invention, it is characterised in that step 1) pentaerythritol diacrylate
Alkali used in chloracetyl chloride (IV) reaction process is replaced to be selected from tertiary amine, secondary sterically hindered amines with alkyl；It is preferred that triethylamine, tripropyl amine (TPA), two
Diisopropylethylamine.Pentaerythritol diacrylate and alkyl replace chloracetyl chloride (IV) to feed intake the mass ratio of the material selected from 1:
1.05-1.5.Step 1) reaction temperature is selected from -10-0 DEG C.
The preparation method of formula (I) compound provided by the invention, it is characterised in that the catalyst of esterification in step 2)
Selected from alkali compounds, preferably potassium carbonate, triethylamine.Formula (II) compound and 4- thioxanthones formic acid the mass ratio of the material are selected from 1-
1.1:1；The mass ratio of the material of catalyst and 4- thioxanthones formic acid is selected from 1.1-2:1；The reaction temperature of step 2) ester is selected from 45-75
℃。
The preparation method of formula (I) compound provided by the invention, it is characterised in that polymerization inhibitor used in step 2) is selected to benzene
Diphenol, p-hydroxyanisole, BHT, anhydrous cupric sulfate, additive amount are selected from 100~10000ppm.
The preparation method of formula (I) compound provided by the invention, it is also possible to which following reaction equations carry out:
Wherein: R is selected from H, C1-C4 alkyl.
The preparation method of formula (I) compound provided by the invention can also comprise the following steps that
1) 4- thioxanthones formic acid replaces methyl chloroacetate (V) to react generation formula (III) chemical combination under alkaline condition with alkyl
Object；
2) above-mentioned formula (III) compound 1) obtained under the action of catalyst and polymerization inhibitor with corresponding pentaerythrite two
Acrylate esterification reaction, obtains formula (I) compound.
Alkali used in step 1) 4- thioxanthones formic acid and methyl chloroacetate reaction process is selected from tertiary amine, secondary sterically hindered amines；It is preferred that
Triethylamine, tripropyl amine (TPA), diisopropyl ethyl amine.4- thioxanthones formic acid and alkyl replace methyl chloroacetate (V) to feed intake the amount of substance
Than being selected from 1:1.1~2.0, the dosage of alkali is selected from 1.1~1.5 times of the amount of 4- thioxanthones formic acid substance.
The catalyst of step 2) ester exchange reaction is selected from the preferred sodium methoxide of alkali compounds, sodium tert-butoxide, potassium tert-butoxide.Ester
The reaction temperature of exchange is selected from 95~130 DEG C.
The preferred hydroquinone of the polymerization inhibitor of step 2) ester exchange reaction, p-hydroxyanisole, BHT, anhydrous cupric sulfate, addition
Amount preferably is selected from 100~10000ppm.
Formula (I) compound provided by the invention shows excellent light-cured performance, and activity is high, and mobility is low, with
The compatibility of resin is preferable.
Specific embodiment:
The present invention will be further illustrated by following nonlimiting examples.
Embodiment 1:The preparation of compound A
By 48.8g pentaerythritol diacrylate (0.2mol), 23.3g triethylamine (0.21mol) and 240ml methylene chloride
It is added to there-necked flask, electromagnetic agitation reaction, three mouths of there-necked flask are separately connected thermometer, drying tube and fill 46.3g chlorine
The constant pressure funnel of chloroacetic chloride (0.41mol) and 120ml methylene chloride, are slowly added dropwise, temperature is maintained at 0 to -5 at low temperature
Between DEG C, after being added dropwise, room temperature reaction is moved to.TLC monitors end of reaction.Triethylamine hydrochloride is filtered, with unsaturated carbonate hydrogen
Sodium is washed 2-3 times, then is washed with saturated common salt, and anhydrous magnesium sulfate is dry, is spin-dried for.With chromatography column separating purification, Transparent color oily is obtained
Object, yield are about 85%, purity >=95%.1H NMR(400MHz,CDCl3)δ6.45(dd,1H),6.05(m,2H),5.58
(dd, 2H), 4.34 (s, 4H), 4.10 (s, 4H), 4.00 (s, 4H).
Equipped in churned mechanically four mouthfuls of reaction flasks, 102.5g thioxanthones -4- carboxylic acid (0.4mol), 60.8g carbon is added
Sour potassium (0.44mol), 500ml DMF, 79.4g pentaerythrite (two acryloxies) two (2- (2- chloroethene acyloxy) ethyl ester)
(0.2mol), 0.5g hydroquinone are heated to 65 DEG C, and TLC monitors fully reacting.It filters salt while hot to precipitate, filtrate precipitation, slowly
Cool down crystallization, obtains pale yellow crystals 125.6g.1H NMR(400MHz,CDCl3): δ 8.23 (d, 2H), 7.79 (d, 1H), 7.60-
7.28 (m, 10H), 6.25 (d, 2H), 6.05 (m, 2H), 5.59 (d, 2H), 5.21 (s, 4H), 4.12 (s, 4H), 4.00 (s,
4H).MS:m/z [M+1]+=837.
Embodiment 2:The preparation of compound B
By 48.8g pentaerythrite two (acrylic acid) ester (0.2mol), 23.3g triethylamine (0.21mol) and 240ml dichloromethane
Alkane is added to there-necked flask, and electromagnetic agitation reaction, three mouths of there-necked flask are separately connected thermometer, drying tube and fill 51.6g
The constant pressure funnel of 2- chlorpromazine chloride (0.41mol) and 120ml methylene chloride, are slowly added dropwise, temperature is maintained at 0 at low temperature
Between to -5 DEG C, after being added dropwise, room temperature reaction is moved to.TLC monitors end of reaction.Triethylamine hydrochloride is filtered, saturated carbon is used
Sour hydrogen sodium is washed 2-3 times, then is washed with saturated common salt, and anhydrous magnesium sulfate is dry, is spin-dried for.With chromatography column separating purification, Transparent color is obtained
Grease, yield are about 80%, purity >=95%.1H NMR(400MHz,CDCl3)δ6.37(dd,1H),6.15(m,2H),
5.54 (dd, 2H), 4.45 (q, 2H), 4.30 (s, 4H), 4.10 (s, 4H), 4.00 (s, 4H), 1.73 (d, 6H).
Equipped in churned mechanically four mouthfuls of reaction flasks, 102.5g thioxanthones -4- carboxylic acid (0.4mol), 60.8g carbon is added
Sour potassium (0.44mol), 500ml dichloroethanes, (2- (the 2- chlorine propionyloxy) second of 85.1g pentaerythrite two (acryloxy) two
Ester) (0.2mol), 0.6g p-hydroxyanisole is heated to 65 DEG C, and TLC monitors fully reacting.Salt precipitating is filtered while hot, and filtrate is de-
It is molten, with chromatography column separating purification, give light yellow oil 103.8g.1H NMR(400MHz,CDCl3): δ 8.31 (d, 2H), 7.69
(d, 1H), 7.53-7.32 (m, 10H), 6.20 (d, 2H), 6.00 (m, 2H), 5.56 (d, 2H), 5.21 (s, 4H), 4.97 (q,
2H), 4.00 (s, 4H), 1.57 (d, 6H).MS:m/z [M+1]+=865.
Embodiment 3:Preparation
In churned mechanically 500ml four-hole bottle is housed, addition 50.0g thioxanthones -4- carboxylic acid, 250ml tetrahydrofuran,
23.6g triethylamine, 25.6g methyl chloroacetate are heated to 50~60 DEG C and react 8 hours, filter, and filtrate is cooled to 0~5 DEG C of stirring
Crystallization filters to obtain crude product after 2 hours, crude product re crystallization from toluene, obtains 53.7g yellow flat crystal after dry, yield 84%,
Content >=98.0%.
In the 500ml four-hole bottle equipped with mechanical stirring and water segregator, 32.8g thioxanthones -4- formyloxy acetic acid is added
Methyl esters, 0.3g sodium methoxide, 200ml hexahydrotoluene, 13.5g pentaerythritol diacrylate, 0.2g p-hydroxyanisole, heating
Divide methanol 14 hours to reflux.Slow cooling, is precipitated solid, and filtering obtains 24.2g light yellow solid, liquid content >=92%.
MS:m/z [M+1]+=837
Embodiment 4: performance evaluation
Photocurable composition is prepared by the proportion of table 1, using 22 μm of bar spreaders by prepared Photocurable composition
It applies on the glass sheet.On tape by the installation of the sample of coating, under mercury lamp light source under convey the sample.Quarter is pressed to scrape repeatedly with nail
Wiping, which does not generate, is imprinted as being fully cured standard, determines the belt speed that sample is fully cured.
Table 1: photocuring system formula
Comparison A is structure
Comparison B is structure
Comparison C is structure
Comparison D is structure
(segment containing polyethylene glycol 400,)
1, curing rate evaluation result is as shown in table 2:
Table 2: curing rate evaluation result
| Curing rate m/min | |
| 1 group | 25 |
| 2 groups | 20 |
| 3 groups | 35 |
| 4 groups | 30 |
| 5 groups | 25 |
| 6 groups | 45 |
The photoinitiator of the application preparation has good curing rate compared to comparison initiator as can be seen from Table 2.
2, migration evaluation
It weighs EO3-TMPTA solution 0.5g, ultrasonic 30min that initiator quality score is 3% and is uniformly coated on glass
On piece (25mm × 75mm), with a thickness of 100um, 3-5min is irradiated under mercury lamp, it is fully cured.Unified mass film will be had
Glass plate be immersed in the brown, wide-mouth bottle for filling the chloroform of 50ml, impregnate 4d.After immersion, UV absorption spectrum is tested.
According to the following formula, the mobility of embodiment polymerizable photoinitiator and reference material initiator is obtained:
C=A/ (ε L) ... ... ... ... ... ... (1)
X=m1/m2.……..………………………(2)
Wherein: the concentration of initiator, mol/L in C-extract liquor；
A-absorbance；
ε-molar extinction coefficient, L/ (molcm)；
L-optical path length, cm；
X-retained percentage, %；
m1The residual mass of-initiator, g；
m2The quality of-addition initiator, g
As a result as shown in table 3:
Table 3: initiator remains evaluation result
| Initiator residual percentage/% | |
| Compound A | 0.09 |
| Compound B | 0.07 |
| Comparison A | 1.10 |
| Comparison B | 0.80 |
| Comparison C | 0.15 |
| Comparison D | 0.23 |
Claims (4)
1. a kind of polymerizable photoinitiator, structural formula is (I):
Wherein: R is selected from H, C1-C4 alkyl.
2. polymerizable photoinitiator according to claim 1, it is characterised in that formula (I) is selected from having structure:
。
3. polymerizable photoinitiator according to claim 1, it is characterised in that prepared through the following steps:
Wherein: R is selected from H, C1-C4 alkyl,
1) pentaerythritol diacrylate replaces chloracetyl chloride (IV) to react generation formula (II) chemical combination under alkaline condition with alkyl
Object；
2) the above-mentioned formula (II) compound 1) obtained under the action of catalyst and polymerization inhibitor with corresponding 4- thioxanthones formic acid esters
Change reaction, obtains formula (I) compound；
Wherein step 1) pentaerythritol diacrylate and alkyl replace alkali used in chloracetyl chloride (IV) reaction process to be selected from uncle
Amine, secondary sterically hindered amines；It is preferred that triethylamine, tripropyl amine (TPA), diisopropyl ethyl amine；Pentaerythritol diacrylate and alkyl replace chloroethene
Acyl chlorides (IV) feeds intake the mass ratio of the material selected from 1:1.05-1.5；Step 1) reaction temperature is selected from -10-0 DEG C；
The catalyst of esterification is selected from alkali compounds, preferably potassium carbonate, triethylamine in step 2；Formula (II) compound and 4-
Thioxanthones formic acid the mass ratio of the material is selected from 1-1.1:1；The mass ratio of the material of catalyst and 4- thioxanthones formic acid is selected from 1.1-2:1；
The reaction temperature of step 2 ester is selected from 45-75 DEG C；Polymerization inhibitor used in step 2 be selected from hydroquinone, p-hydroxyanisole, BHT,
Anhydrous cupric sulfate, additive amount are selected from 100 ~ 10000ppm.
4. polymerizable photoinitiator according to claim 1, it is characterised in that prepared through the following steps:
Wherein: R is selected from H, C1-C4 alkyl；
1) 4- thioxanthones formic acid replaces methyl chloroacetate (V) to react generation formula (III) compound under alkaline condition with alkyl；
2) the above-mentioned formula (III) compound 1) obtained under the action of catalyst and polymerization inhibitor with corresponding two propylene of pentaerythrite
Acid esters esterification obtains formula (I) compound；
Alkali used in step 1) 4- thioxanthones formic acid and methyl chloroacetate reaction process is selected from tertiary amine, secondary sterically hindered amines；It is preferred that three second
Amine, tripropyl amine (TPA), diisopropyl ethyl amine；4- thioxanthones formic acid and alkyl replace methyl chloroacetate (V) to feed intake the mass ratio of the material choosing
From 1:1.1 ~ 2.0, the dosage of alkali is selected from 1.1 ~ 1.5 times of the amount of 4- thioxanthones formic acid substance；
The catalyst of step 2 ester exchange reaction is selected from the preferred sodium methoxide of alkali compounds, sodium tert-butoxide, potassium tert-butoxide；
The reaction temperature of transesterification is selected from 95 ~ 130 DEG C；
The preferred hydroquinone of the polymerization inhibitor of step 2 ester exchange reaction, p-hydroxyanisole, BHT, anhydrous cupric sulfate, additive amount are excellent
Selected from 100 ~ 10000ppm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022207945A3 (en) * | 2021-10-08 | 2022-12-01 | Igm Resins Italia S.R.L. | "novel photoinitiators" |
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|---|---|---|---|---|
| JP2009221439A (en) * | 2008-03-19 | 2009-10-01 | Toyo Ink Mfg Co Ltd | Photocurable inkjet ink |
| EP2205582B1 (en) * | 2007-11-09 | 2012-07-18 | Lambson Limited | Multi-functional thioxanthone photoinitiators |
| CN104910131A (en) * | 2015-06-23 | 2015-09-16 | 天津久日化学股份有限公司 | New thioxanthone carboxylic ester photoinitiator and preparation method thereof |
| CN107629151A (en) * | 2017-10-27 | 2018-01-26 | 天津久日新材料股份有限公司 | A kind of type light trigger of polymerizable free radical II and preparation method thereof |
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2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2205582B1 (en) * | 2007-11-09 | 2012-07-18 | Lambson Limited | Multi-functional thioxanthone photoinitiators |
| JP2009221439A (en) * | 2008-03-19 | 2009-10-01 | Toyo Ink Mfg Co Ltd | Photocurable inkjet ink |
| CN104910131A (en) * | 2015-06-23 | 2015-09-16 | 天津久日化学股份有限公司 | New thioxanthone carboxylic ester photoinitiator and preparation method thereof |
| CN107629151A (en) * | 2017-10-27 | 2018-01-26 | 天津久日新材料股份有限公司 | A kind of type light trigger of polymerizable free radical II and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022207945A3 (en) * | 2021-10-08 | 2022-12-01 | Igm Resins Italia S.R.L. | "novel photoinitiators" |
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